The present invention relates to a resin composition comprising a fluorinated polymer having a high fluorine content and a polymer containing no fluorine, which are uniformly and finely dispersed and mixed by a dispersing agent.
Heretofore, fluorinated polymers represented by a tetrafluoroethylene polymer, are excellent in heat resistance, flame retardant properties, chemical resistance, weather resistance, anti-sticking properties, low frictional properties and low dielectric properties, and used in a wide range of fields including, for example, a coating material for heat-resistant flame-retardant electrical wires, a corrosion-resistant piping material for chemical plants, a material for agricultural vinyl film houses, and a mold release coating material for kitchen equipment.
Such properties are derived from the three points of a strong C-F bond, a small polarizability and a weak intermolecular cohesion energy. Particularly, a low intermolecular cohesion energy makes the surface energy of the polymer low, whereby the affinity with another material, particularly with a polymer containing no fluorine, is low. Accordingly, a composition comprising a fluorinated polymer and a polymer containing no fluorine, one of which is uniformly and finely dispersed in the other polymer, can not be obtained.
To overcome this problem, the present inventors have proposed a composition comprising a fluorinated polymer, a non-fluorinated polymer, and as a dispersing agent, a grafted polymer obtained by reacting a fluorinated polymer having hydrogen atoms bonded to carbon atoms in its main chain, with a vinyl monomer having a functional group, while generating radicals, before (JP-A-9-118802).
This dispersing agent is effective for a fluorinated polymer having a low fluorine content, such as one having hydrogen atoms bonded to carbon atoms in its main chain in a certain proportion. However, there is a limitation for uniformly and finely dispersing a non-fluorinated polymer with a polymer having a high fluorine content, or with a polymer containing substantially no hydrogen atom bonded to carbon atoms in its main chain.
The present invention has been made to overcome the above-mentioned problems. The present inventors have found that a fluorine-containing resin composition comprising a polymer having a high fluorine content and a non-fluorinated polymer containing no fluorine, which are uniformly and finely dispersed and mixed, can be obtained, by using a fluorinated compound having, as a functional group, a carboxylic acid group or its derivative, or a sulfonic acid group or its derivative, in its molecule, as a dispersing agent to disperse and mix the polymers, and the present invention has been accomplished.
Namely, the present invention provides a fluorine-containing resin composition which comprises, in 100 parts by weight of the composition, from 2 to 89 parts by weight of a fluorinated polymer (a) which has a fluorine content of at least 65 wt % in its polymer molecule (hereinafter referred to as fluorinated polymer (a)), from 97 to 10 parts by weight of a polymer (b) containing no fluorine (hereinafter referred to as non-fluorinated polymer (b)), and from 1 to 35 parts by weight of a functional group-containing fluorinated compound (c) having, as a functional group, a carboxylic acid group or its derivative, or a sulfonic acid group or its derivative, in its molecule.
Here, the fluorinated polymer (a) has neither carboxylic acid group or its derivative, nor sulfonic acid group or its derivative, in its molecule, and it is different from the functional group-containing fluorinated compound (c).
The composition of the present invention has an island structure in which depending upon the amounts of the fluorinated polymer (a) and the non-fluorinated polymer (b) to be blended, the component with a smaller blending amount is dispersed in the other component. Accordingly, in the present invention, the component to be dispersed uniformly and finely, is not limited, and the structure of the composition may be such that the fluorinated polymer (a) is dispersed in the non-fluorinated polymer (b), or the structure may be such that the non-fluorinated polymer (b) is dispersed in the fluorinated polymer (a).
As the fluorinated polymer (a) to be used in the present invention, a fluorinated polymer having a fluorine content of at least 65 wt % in its polymer molecule is used. Further, in view of heat resistance of the polymer, a polymer having a fluorine content of at least 70 wt % is preferably used.
As a preferred fluorinated polymer (a), a homopolymer of a fluoroolefin selected from tetrafluoroethylene (hereinafter referred to as TFE) and chlorotrifluoroethylene (hereinafter referred to as CTFE), or a copolymer of a fluoroolefin with a fluorinated monomer such as perfluoro(alkyl vinyl ether), hexafluoropropylene (hereinafter referred to as HFP), vinylidene fluoride or vinyl fluoride, may be used. Further, a copolymer of the above-mentioned fluoroolefin with an xcex1-olefin containing no fluorine such as ethylene, propylene or butene, may be used, so long as the fluorine content in its polymer is at least 65 wt %.
As a specific example of such a fluorinated polymer, a TFE polymer (hereinafter referred to as PTFE), a CTFE polymer (hereinafter referred to as PCTFE), a TFE-HFP copolymer (hereinafter referred to as FEP), a TFE-perfluoro (alkyl vinyl ether) copolymer (hereinafter referred to as PFA), a TFE-ethylene copolymer (hereinafter referred to as ETFE), a CTFE-ethylene copolymer or a TFE-propylene copolymer may, for example, be mentioned. Preferred is PTFE, PCTFE, FEP or PFA, and particularly preferred is PFA, in view of heat resistance and chemical stability.
The non-fluorinated polymer (b) to be used in the present invention is a polymer containing no fluorine atom in its molecule.
The non-fluorinated polymer (b) is preferably a heat-resistant polymer capable of being melted and mixed with a fluorinated polymer having a high heat resistance. It is particularly preferably a polymer having a glass transition point (Tg) of at least 140xc2x0 C. as an index of the heat resistance. As a specific example of the non-fluorinated polymer (b), an engineering plastic such as a polyamide (hereinafter referred to as PA), a polyamidoimide (hereinafter referred to as PAI), a polyetherimide (hereinafter referred to as PEI), a thermoplastic polyimide, a polycarbonate (hereinafter referred to as PC), a polysulfone (hereinafter referred to as PSF), a polyether sulfone (hereinafter referred to as PES), a polyether ether ketone (hereinafter referred to as PEEK), a polyallylate (hereinafter referred to as PAR), a modified PPO, a reinforced PET or a liquid crystal polymer (hereinafter referred to as LCP) may, for example, be mentioned. Among these, particularly preferred is PEI, PAI, a polybismaleimide, a thermoplastic polyimide or PES, and most preferred is PEI.
The contents of these fluorinated polymer (a) and non-fluorinated polymer (b) is such that in 100 parts by weight of the composition, the fluorinated polymer (a) is from 2 to 89 parts by weight, preferably from 10 to 44 parts by weight, and the non-fluorinated polymer (b) is from 97 to 10 parts by weight, preferably from 89 to 55 parts by weight.
In the present invention, as a dispersing agent, a functional group-containing fluorinated compound (c) having, as a functional group, a carboxylic acid group or its derivative, or a sulfonic acid group or its derivative, in its molecule (hereinafter referred to as dispersing agent (c)) is used. By using the dispersing agent (c), a composition having a structure in which the above-mentioned (a) and (b) are uniformly and finely dispersed, can be obtained. The composition of the present invention can not be obtained by simply blending (a) and (b). Such a dispersing agent can commonly be available as a surface active agent. Further, in view of the affinity with the fluorinated polymer (a), a compound containing fluorine is preferably used.
As a specific example of the dispersing agent (c) having, as a functional group, a carboxylic acid group or its derivative in its molecule, a perfluoroalkyl carboxylic acid such as C7F15COOH, C8F17COOH, C9F19COOH, C10F21COOH, C11F23COOH or C12F25COOH, or its alkyl ester compound such as a methyl ester and an ethyl ester, its alkali metal salt or its ammonium salt, may, for example, be mentioned. Further, a polyfluoroalkyl carboxylic acid having some of fluorine atoms in the perfluoroalkyl group of the above-mentioned compound substituted by hydrogen atoms or other halogen atoms, or its derivative may, for example, be mentioned.
Further, as another specific example of the dispersing agent (c), a perfluoroalkyl ether carboxylic acid such as C3F7OCF(CF3)COOH and C3F7OCF(CF3)CF2OCF(CF3)COOH, or its alkyl ester compound such as a methyl ester or an ethyl ester, its alkali metal salt or its ammonium salt, may, for example, be mentioned. Further, a polyfluoroalkyl carboxylic acid having some of fluorine atoms in the perfluoroalkyl group in the above-mentioned compound substituted by hydrogen atoms or other halogen atoms, or its derivative may, for example, be mentioned.
Still further, as another specific example of the dispersing agent (c), a perfluoroalkyl dicarboxylic acid such as C4F8(COOH)2, C6F12(COOH)2 or C8F16(COOH)2, or its alkyl ester compound such as a methyl ester or an ethyl ester, its alkali metal salt or its ammonium salt, may, for example, be mentioned. Further, a polyfluoroalkyl carboxylic acid having some of fluorine atoms in the perfluoroalkyl group of the above-mentioned compound substituted by hydrogen atoms or other halogen atoms, or its derivative may, for example, be mentioned.
Further, as a specific example of the dispersing agent (c) having, as a functional group, a sulfonic acid group or its derivative in its molecule, a series of the above-mentioned compounds having the carboxylic acid group substituted by a sulfonic acid group, may be mentioned.
In the present invention, in view of dispersibility, the dispersing agent (c) is most preferably a fluorinated polymer containing polymer units based on an ethylene type monomer (hereinafter referred to as monomer (1)) having, as a functional group, at least one type of a carboxylic acid group or its derivative, or a sulfonic acid group or its derivative, in its molecule.
Here, in view of heat resistance, the monomer (1) having a carboxylic acid group or its derivative in its molecule is preferably a fluorinated monomer.
As a preferred specific example of the monomer (1) having a carboxylic acid group or its derivative in its molecule, a monomer having an ethylene type polymerizable functional group and a carboxylic acid group, such as CF2xe2x95x90CFOCF2CF2CF2COOH, CF2xe2x95x90CFOCF2CF2COOH, CF2xe2x95x90CFOCF2CF(CF3)OCF2CF2COOH or CH2xe2x95x90CHCF2CF2CF2COOH, or its alkyl ester compound such as a methyl ester or an ethyl ester, its alkali metal salt or its ammonium salt, may, for example, be mentioned.
As a preferred specific example of the monomer (1) having, as a functional group, a sulfonic acid group or its derivative in its molecule, a monomer having an ethylene type polymerizable functional group and a sulfonic acid group, such as CF2xe2x95x90CFOCF2CF2CF2SO3H, CF2xe2x95x90CFOCF2CF2SO3H, CF2xe2x95x90CFOCF2CF(CF3)OCF2CF2SO3F or CH2xe2x95x90CHCF2CF2CF2SO3H, or its alkyl ester compound such as a methyl ester or an ethyl ester, its alkali metal salt, its ammonium salt or its halide may, for example, be mentioned.
As a polymer of such a monomer (1), a homopolymer of the above-mentioned monomer (1), a copolymer of at least two types of the above-mentioned monomers (1) or a copolymer of the above-mentioned monomer (1) with an ethylene type monomer (hereinafter referred to as monomer (2)) copolymerizable with the above-mentioned monomer (1), may be used.
As the ethylene type monomer (2), an xcex1-olefin such as ethylene or propylene, a vinyl ether or a vinyl ester may be mentioned. Preferred is an ethylene type fluorinated monomer having some or all hydrogen atoms in such a monomer substituted by fluorine atoms. As a preferred specific example of the monomer (2), TFE, CTFE, HFP or a perfluoro(alkyl vinyl ether) may, for example, be mentioned. The monomer (2) may be used alone or in combination as a mixture of two or more of them.
In the copolymer of the above-mentioned monomer (1) and monomer (2), the ratio of polymer units based on the monomer (1) is preferably from 3 to 30 mol %, more preferably from 3 to 15 mol %. If the ratio of the polymer units based on the monomer (1) is small, the effect as a dispersing agent is small, and if the ratio is large, the effect as a dispersing agent is also small.
The molecular weight of the polymer of the dispersing agent (c) is not particularly limited. However, it is preferably high within a range of not exceeding the molecular weight of the fluorinated polymer (a) to be used. If the molecular weight of the dispersing agent (c) is higher than the fluorinated polymer (a), melt-processing properties of the obtained composition may decrease, in some cases. Further, if the molecular weight of the dispersing agent (c) is extremely low, heat stability of the dispersing agent itself may decrease, whereby the dispersing effect can not be obtained, in some cases.
The polymer of the dispersing agent (c) can be produced by a common radical polymerization method. Further, as the polymerization type, an emulsion polymerization, a solution polymerization or a suspension polymerization may, for example, be employed.
The content of the dispersing agent (c) is from 1 to 35 parts by weight, preferably from 5 to 32 parts by weight, in 100 parts by weight of the composition. If the content of the dispersing agent (c) is less than 1 part by weight, the dispersibility of the mixture tends to be low, and if it exceeds 35 parts by weight, mechanical properties of the composition tends to deteriorate due to the dispersing agent (c), such being unfavorable.
The composition of the present invention can be produced by melt-mixing the components. It is preferred to mechanically knead the components at the temperature at which all the components are melted. The melt-mixing can be carried out by using e.g. a high temperature kneader or a screw extruder. Preferably, a twin-screw extruder is used, to carry out the mixing more vigorously.
The fluorine-containing resin composition of the present invention can be applied, as a molding material, to production of various molded products. In such a case, various types of fillers such as an inorganic powder, glass fibers, carbon fibers, a metal oxide and carbon, may be blended with the fluorine-containing resin composition of the present invention, within a range of not impairing the performances. Further, other than the fillers, optional additives such as a pigment, an ultraviolet absorber, a photostabilizer and an antioxidant, may be blended with the fluorine-containing resin composition of the present invention, depending upon the application.
By using the fluorine-containing resin composition of the present invention as a molding material, a molded product can be produced by a known molding method such as an injection molding, an extrusion molding, a co-extrusion molding, an inflation molding, coating or a transfer molding using a mold.
Further, the fluorine-containing resin composition of the present invention is uniformly and finely dispersed, and accordingly the obtained molded product is excellent in mechanical properties. Particularly, a composition of the fluorinated polymer (a) and the non-fluorinated polymer (b) which are uniformly and finely dispersed, having a high impact strength of the obtained molded product, can be obtained.